This chapter describes the electrochemistry of the porphyrins at solid-liquid and liquidliquid interfaces. The fundamental electrochemical approach toward the porphyrin molecules in estimating their HOMO and LUMO energy levels is given. Various factors such as the effect of central metal ion, the periphery of the aromatic ring and axial ligands on the redox potentials of porphyrins have been discussed. Electrochemical sensing application of porphyrin molecules is described with few examples in brief. Much focus has been given on the electrochemistry of the self-assembled monolayer (SAM) of thiol-porphyrins on the gold electrode. Structural characterization and charge transfer across the SAM using cyclic voltammetry and electrochemical impedance spectroscopy are discussed. Theory and methodologies developed to study photoinduced charge transfer kinetics of porphyrin molecules using scanning electrochemical microscope at the solid-liquid and liquid-liquid interface have been described. Use of porphyrin molecules as luminophores in electrochemiluminescence sensing applications and the mechanisms involved are described through representative examples.